chromatographic characteristics and identification of ...

on Dicyclopentadiene” and by the project of the Ministry of Education, Youth and Sports,CEZ: MSM 6046137301.Table 6. List of dimers and codimers with unambiguous assigned chemical structureDiels-AlderproductJiří Krupka, Josef Pašek/Petroleum&Coal 52(4) 227-234, 2010 231Compound nameRT [min]HP-PONAtemp.prog.RIHP-PONA100°CMDCPD KOD C 7-MDCPD *(7-methyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoindene) 19.44 1042.4MDCPD KOD B 4-MDCPD ** 19.55 1046.5MDCPD 1 5-MDCPD 20.62 1084.3MDCPD 2 2-MDCPD 20.81 1090.7MDCPD 3 3-MDCPD 21.04 1098.9DMDCPD 1 2,7-DMDCPD ** 21.22 1104.2DMDCPD 3 endo-2,4-DMDCPD 21.26 1104.8DMDCPD 4 endo-3,7-DMDCPD 21.35 1108.6DMDCPD 5 endo-2,5-DMDCPD 21.48 1112.8DMDCPD 6 endo-3,4-DMDCPD 22.08 1134.4DMDCPD 7 endo-2,6-DMDCPD 22.11 1134.4DMDCPD 8 3,6-DMDCPD 22.60 1154.1DMDCPD 9 endo-3,5-DMDCPD 22.83 1160.8* ) Position numbering in accordance with IUPAC rule A-34 (3a,4,7,7a-tetrahydro-1H-4,7-methanoindene). ** ) The endo/exo stereoisomeric configuration was not confirmed forsome isomers, however, based on the current knowledge it is possible to consider themcompounds with endo-DCPD skeletonSymbolsCPD1,3-cyclopentadieneDCPDdicyclopentadiene, 3a,4,7,7a-tetrahydro-1H-4,7-methanoindeneDMDCPD dimethyldicyclopentadieneMCPDmethyl-1,3-cyclopentadiene isomerMDCPDmethyldicyclopentadieneMDCPD KOD C methylcyclopentadiene isomer with the shortest retention timeMDCPD KOD B methylcyclopentadiene isomer with the second shortest retention timeRIKovats retention indexΔRIretention index difference compared to the endo-dicyclopentadienereference materialRT retention time [min] under the analysis conditions shown in Table 1References[1] Csicsery, S. M.: J. Org. Chem. 1960, 25, 518.[2] Krupka, J., Štěpánek, K., Herink, T.: Chem. Listy 2008, 102, 1107.[3] Diez, M. S., Fananas, F. J., Blanco, C. G., Bermejo J.: J. Chromatogr. 1989, 464, 93.[4] Diez, M. S., Fananas, F. J., Blanco, C. G., Bermejo J.: J. Chem. Technol.Biotechnol. 1990, 48, 173.[5] Diez, M. S., Guillen, M. D., Blanco, C. G., Bermejo, J.: J. Chromatogr. 1990, 508, 363.[6] Bermejo, J., Blanco, C. G., Diez, M. A.: Afinidad 1983, 40, 320.[7] Lauer, J. C., Laurens, T., Schmit-Quiles, F., Nicole, D., Matlengiewicz, M., Henzel,N.: Analusis 1993, 21, 359.[8] Laurens, T., Nicole, D., Rubini, P., Lauer, J. C., Matlengiewicz, M., Henzel, N.:Magn. Reson. Chem. 1991, 29, 1119.[9] Schmit-Quiles, F., Laurens, T., Nicole, D., Lauer, J. C., Henzel, N.: Analusis 1993,21, 227.[10] Thommen, W., Pamingle, H., Schulte-Elte, K. H.: Helv. Chim. Acta 1989, 72, 1346.[11] Zharov, V. P., Montanari, S. G., Tumanova, L. M.: Zh. Anal. Khim. 1984, 39, 551.[12] Sergeyev, M. N., Avramenko, G. I., Korenevsky, V. A., Ustynyuk, Y. A.: Org.Magn. Reson. 1972, 4, 39.[13] Langer, S. H., Melton, H. R., Griffit, T. D.: J. Chromatogr. 1976, 122, 487.

Jiří Krupka, Josef Pašek/Petroleum&Coal 52(4) 227-234, 2010 232[14] Arefyev, O. A., Vorobyeva, N. S., Epishev, I. V., Petrov, A. A.: Neftekhimiya 1972,12(2), 171.[15] Musaev, M. R., Sharifova, S. M., Aliev, M. A.: Azerbaidzhanskii Khim. Zh. 1975 (5), 43.[16] Mironov, V. A., Fadeeva, T. M., Stepanyanc, A. U., Akhrem, A. A.: Izvestiya Akad.Nauk SSSR Ser. Khim. 1967 (2), 434.[17] Alder, K., Ache, H. J.: Chem. Ber. 1962, 95, 503.[18] Bermejo, J., Blanco, C. G., Diez, M. A., Guillen, M. D.: J. High ResolutionChromatogr. Chromatogr. Commun. 1989, 10, 461.[19] Ruman, J., Soják, L., Holbová, E.: Ropa a Uhlie 1987, 29, 98.

Jiří Krupka, Josef Pašek/Petroleum&Coal 52(4) 227-234, 2010 233Table 2. Comparison of experimental data for methylcyclopentadiene dimerisation with data reported by Diez et al. [5]Experimental data Published data [5]Peak label RT [min]HP-PONAtemp. prog.RIHP-PONA100°CCompound name RIOV-101100°CRIOV-170180°CDMDCPD 3 21.35 1108.6 endo-2,4-(or 2,7-)DMDCPD * 1107.6 1135.3DMDCPD 5 22.08 1134.4 endo-2,5-(or 2,6-)DMDCPD 1133.9 1131.6DMDCPD 6 22.11 1134.4 endo-3,4-(or 3,7-)DMDCPD 1133.9 1166.6DMDCPD 9 22.83 1160.8 endo-3,5-(or 3,6-)DMDCPD 1159.9 1191.3Reference 19.06 1026 endo-DCPD 1025.3 1065.5material* ) Position numbering in accordance with IUPAC rule A-34 (3a,4,7,7a-tetrahydro-1H-4,7-methanoindene).Table 3. Comparison of experimental data for methylcyclopentadiene dimerisation with data reported by Lauer et al. [7]Experimental data Published data [7]Peak label RT [min]HP-PONAtemp. prog.RIHP-PONA100°CΔRI vs.endoDCPDIsomer ratio in Compoundcommercial nameproduct **RICP-SIL19CBprog.ΔRI vs.endoDCPDIsomer ratioin commercialproduct ***DMDCPD 1 21.22 1104.2 78 1.3 2,7-DMDCPD * 1130 73 2.0DMDCPD 2 21.26 1104.8 79 0.5 5,7a-DMDCPD 1127 70 0.2DMDCPD 3 21.35 1108.6 83 5.3 2,4-DMDCPD 1135 78 6.65DMDCPD 4 21.48 1112.8 87 3.3 3,7-DMDCPD 1142 85 3.9DMDCPD 5 22.08 1134.4 108 32.0 2,5-DMDCPD 1162 105 29.8DMDCPD 6 22.11 1134.4 108 3.7 3,4-DMDCPD 1167 110 11.8DMDCPD 7 22.28 1143.0 117 1.0 2,6-DMDCPD 1173 116 1.2? DMDCPD 22.36 1145.7 120 0.10 ?,?-DMDCPD 1177 120 0.05DMDCPD 8 22.60 1154.1 128 1.3 3,6-DMDCPD 1187 130 1.25DMDCPD 9 22.83 1160.8 135 36.2 3,5-DMDCPD 1193 136 39.7? DMDCPD 22.94 1167.7 142 0.17 ?,?-DMDCPD 1199 142 0.16Reference 19.06 1026 0 endo-DCPD 1057 0material* ) Position numbering in accordance with IUPAC rule A-34 (3a,4,7,7a-tetrahydro-1H-4,7-methanoindene).** ) DMDCPD Aldrich.*** ) DMDCPD Fluka.

Jiří Krupka, Josef Pašek/Petroleum&Coal 52(4) 227-234, 2010 234Table 4. Comparison of experimental data for methylcyclopentadiene dimerisation with data reported by Thommen et al. [10]Experimental data Published data [10]Peak label RT [min]HP-PONAtemp.prog.Isomer ratioindimerisationproduct(25°C)Isomer ratioindimerisationproduct(120°C, 2 h)Isomer ratioincommercialproduct**CompoundnameIsomer ratio indimerisationproduct(20°C)DMDCPD 3 21.35 3.05.3 endo-2,4-96.6DMDCPD *DMDCPD 4 21.48 1.63.3 endo-3,7-44.3DMDCPDDMDCPD 5 22.08 24.632.0 endo-2,5-2237.4DMDCPDDMDCPD 6 22.11 3.73.7 endo-3,4-241.1DMDCPDDMDCPD 7 22.28 0.21.0 endo-2,6-11.3DMDCPDDMDCPD 9 22.83 3636.2 endo-3,5-3636DMDCPD* ) Position numbering in accordance with IUPAC rule A-34.** ) DMDCPD Aldrich.*** ) Technical DMDCPD Exxon.Isomer ratioindimerisationproduct(110°C, 3h)75424136Isomer ratioincommercialproduct***532910236Table 5. Identification of cyclopentadiene–methylcyclopentadiene codimer structuresExperimental data Data reported by Lauer et al. [7]Peak label RT [min]HP-PONAtemp.prog.RIHP-PONA100°CΔRI vs.endoDCPDIsomer ratio in Compoundreactionnamemixture(120°C) **RICP-SIL19CBprog.ΔRI vs.endoDCPDIsomer ratio inreactionmixture(70°C) **MDCPD KOD C 19.44 1042.4 16 1.2 7-MDCPD * 1068 11 1.6MDCPD KOD B 19.55 1046.5 21 3.4 4-MDCPD 1073 16 2.8? MDCPD 19.61 1048.7 23 0.14? MDCPD 19.69 1051.2 25 0.2 ?-MDCPD 1078 21 0.2? MDCPD 19.83 1056.0 30 0.07 ?-MDCPD 1084 27 0.1MDCPD 1 20.62 1084.3 58 14.7 5-MDCPD 1113 56 17.0MDCPD 1a 20.69 1085.6 60 1.0 ?-MDCPD 1115 58 0.9MDCPD 2 20.81 1090.7 65 8.2 2-MDCPD 1121 64 11.1MDCPD 3 21.04 1098.9 73 13.9 3-MDCPD 1133 76 13.7Reference material 19.06 1026 0 32.7 endo-DCPD 1057 0 22.6* ) Position numbering in accordance with IUPAC rule A-34.** ) Mixture of CPD, 1-MCPD and 2-MCPD brought to a certain temperature.